CN103897668B - A kind of high temperature heat transfer material based on carbonate and preparation method thereof - Google Patents
A kind of high temperature heat transfer material based on carbonate and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000012546 transfer Methods 0.000 title claims abstract description 54
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 32
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 16
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 16
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 16
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 16
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 16
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229940072033 potash Drugs 0.000 claims abstract description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 15
- 235000015320 potassium carbonate Nutrition 0.000 claims abstract description 15
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- 229940008015 lithium carbonate Drugs 0.000 claims abstract description 6
- 229940001593 sodium carbonate Drugs 0.000 claims abstract description 6
- 238000009413 insulation Methods 0.000 claims description 8
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims 1
- 230000008859 change Effects 0.000 abstract description 9
- 230000007704 transition Effects 0.000 abstract description 9
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000007788 liquid Substances 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 28
- 238000012360 testing method Methods 0.000 description 21
- 230000000630 rising effect Effects 0.000 description 12
- 238000005338 heat storage Methods 0.000 description 10
- 239000011232 storage material Substances 0.000 description 9
- 230000009466 transformation Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 5
- 238000002076 thermal analysis method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- VWXXCBQTSLRHOT-UHFFFAOYSA-K lithium hydrogen carbonate manganese(2+) carbonate Chemical compound C([O-])([O-])=O.[Li+].C([O-])(O)=O.[Mn+2] VWXXCBQTSLRHOT-UHFFFAOYSA-K 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 239000012782 phase change material Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Processing Of Solid Wastes (AREA)
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Abstract
The present invention relates to a kind of high temperature heat transfer material based on carbonate, it is prepared from by raw material manganese carbonate, lithium carbonate, potash, sodium carbonate, and the shared mass percent of each raw material is: manganese carbonate 25%-40%, lithium carbonate 45%-60%, potash 9%-20%, sodium carbonate 9%-15%. This high temperature heat transfer material has the features such as latent heat of phase change is high, phase transition temperature is low, liquid fluidity is good, can be widely used in industrial heat energy recycling, solar thermal utilization etc.
Description
Technical field
The present invention relates to a kind of high temperature heat transfer material based on carbonate and preparation method thereof, be applied to industrial heat energy recycle,Solar thermal utilization etc.
Background technology
The utilization of the energy is the basis that people depends on for existence, along with the accelerated development of global suitability for industrialized production, and the exploitation of the energyMore and more receive people's concern with day by day serious problem of environmental pollution. Devoting Major Efforts To Developing regenerative resource is to solve energy problemImportant channel. The heat utilization of solar energy has unlimitedness, generality and the feature of environmental protection, solar radiation heat energy is stored, by the timeWhen needs, release heat is utilized again, and heat accumulation is an indispensable link. This process is dived to the phase transformation of phase-change heat-storage materialThe hot physical property such as heat, specific heat capacity and storage density have higher requirement.
High-temperature phase-change heat storage material, in the time of charging process, stores the heat of absorption; When exothermic process, phase-change material solidifiesRelease heat is to heat transfer medium, to realize the transmission utilization of heat energy. Fuse salt has that latent heat of phase change is large, phase transition temperature is low, costThe advantages such as low, serviceability temperature scope is wide, have very large researching value in the application of high temperature. Document 1 (SandiaNationalLaboratories.SolarPowerTowerDesignBasisDocument[R].California:SandiaCorporation.2001:73-86.) pointed out in SolarTwo solar power plant ripe employing sodium nitrate and potassium nitrateSalt-mixture as conduct heat and heat-storing material. Document 2 (Sun Liping, Wu Yuting, Ma Chongfang. solar energy high temperature accumulation of heat fuse salt is excellentFirst experimental study [J]. solar energy journal, 2008 (9): 29-9.) molten to anhydrous chlorides of rase sodium, anhydrous magnesium chloride, anhydrous potassium chloride etc.Specific heat capacity and the fusing point of salt are measured. Document 3 (PengQ, DingJ, WeiX, YangJ, YangX.ThepreparationAndpropertiesofmulti-componentmoltensalts.AppliedEnergy2 010,87:2812-2817.) report usedA kind of temperature can reach the fused salt of 550 DEG C. The fuse salt that great majority drop into industrial application is mainly nitrate, chlorate and mixing thereofSalt. The advantage of nitrate is that fusing point is lower, reduces pipeline because solidifying the probability that produces frozen block, and its shortcoming is also comparatively obvious,Under high temperature, in operating temperature, be limited to 600 DEG C, temperature will be decomposed into other materials higher than after serviceability temperature, can not meet high temperatureThe needs of heat generating.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of height based on carbonate for the deficiency of above-mentioned prior art existenceTemperature heat-transfer matcrial and preparation method thereof, this high-temperature phase-change heat storage material latent heat of phase change is large, phase transition temperature is low, phase-change thermal storage ability withThe rising of temperature and constantly strengthen.
The present invention for the technical scheme that the problem of the above-mentioned proposition of solution adopts is:
A high temperature heat transfer material based on carbonate, by raw material manganese carbonate, lithium carbonate, potash, sodium carbonate through mixed meltingPrepare, the shared mass percent of each raw material is respectively: manganese carbonate 25%-40%, lithium carbonate 45%-60%, carbonic acidPotassium 9%-20%, sodium carbonate 9%-15%.
Press such scheme, described manganese carbonate, lithium carbonate, potash, sodium carbonate quality purity are all greater than 99.90%.
The preparation method of the above-mentioned high temperature heat transfer material based on carbonate, comprises the steps:
(1) batching: take by mass percentage manganese carbonate 25%-40%, lithium carbonate 45%-60%, potash 9%-20%,Sodium carbonate 9%-15% is as raw material;
(2) make its fusing after above-mentioned raw materials is mixed in proportion, and in molten condition insulation, it is mixed, finally coolingGrind, obtain the high temperature heat transfer material based on carbonate.
Press such scheme, the temperature of described fusing is 500-600 DEG C.
Press such scheme, described temperature retention time is 18-24h.
Press such scheme, described raw material can carry out drying and processing in advance, does not contain moisture as far as possible. Certainly, if the matter of raw materialAmount purity all can reach 99.90%, does not carry out drying and processing also passable.
Press such scheme, the mixing described in step (2) can adopt the method for mechanical mixture, and it is reached in macroscopic view as far as possibleEvenly.
Press such scheme, the object of the insulation described in step (2) is to make the raw material of molten condition fully mixed by free diffusingClose evenly.
The above-mentioned high temperature heat transfer material based on carbonate can keep stable below 800 DEG C, and its phase transformation operating temperature range is390-800 DEG C, illustrates that this high temperature heat transfer material can be widely used in industrial heat energy recycling, solar thermal utilization etc.
Compared with prior art, the invention has the beneficial effects as follows:
The first, novelty of the present invention be to adopt phase transition temperature 390-400 DEG C taking manganese carbonate lithium carbonate as main quaternary carbonAcid fused salt is as heat accumulation heat-transfer matcrial, and it is excellent that this system has that latent heat of phase change is large, high-temperature stability is strong, toxicity is little, corrosivity is little etc.Point can use as heat accumulation and heat-transfer matcrial simultaneously, has reduced cost in having improved energy conversion efficiency;
The second, utilize mode, carbon in the present invention for operating temperature range the high-temperature solar generating of 600 DEG C-800 DEG CThe liquid phase operating temperature range of acid fused salt can be mated preferably with it, and the mixed carbonate of specific components composition of the present invention can be oneDetermine to reduce fusing point in degree, the operating temperature range of phase-change heat-storage material is effectively increased.
Brief description of the drawings
Fig. 1 is the DSC curve of the prepared high temperature heat transfer material based on carbonate of embodiment 1.
Fig. 2 is the specific heat capacity curve of the prepared high temperature heat transfer material based on carbonate of embodiment 1.
Fig. 3 is the thermogravimetric curve of the prepared high temperature heat transfer material based on carbonate of embodiment 1.
Fig. 4 is the DSC curve of the prepared high temperature heat transfer material based on carbonate of embodiment 2.
Fig. 5 is the specific heat capacity curve of the prepared high temperature heat transfer material based on carbonate of embodiment 2.
Fig. 6 is the DSC curve of the prepared high temperature heat transfer material based on carbonate of embodiment 3.
Fig. 7 is the DSC curve of the prepared high temperature heat transfer material based on carbonate of embodiment 4.
Fig. 8 is the prepared high temperature heat transfer material DSC curve based on carbonate of embodiment 5.
Detailed description of the invention
In order to understand better the present invention, further illustrate content of the present invention below in conjunction with example, but the present invention not only limits toIn the following examples.
Manganese carbonate, lithium carbonate, potash, sodium carbonate quality purity used in following embodiment are all greater than 99.90%.
Embodiment 1
A high temperature heat transfer material based on carbonate, the shared mass percent of the each component of its raw material is: manganese carbonate 35%, carbonic acidLithium 45%, potash 11%, sodium carbonate 9%.
By even above raw material ground and mixed after drying and processing, then the raw material mixing is added to crucible, be placed in resistance furnaceIn, start to be heated to its fusing and be incubated 24 hours at 500 DEG C, to ensure that raw material fully mixes; Insulation is afterwards by crucibleFrom electric furnace, take out coolingly, then pulverize, grind, obtain the high temperature heat transfer material based on carbonate.
Adopt high temperature prepared by STA-449F3 simultaneous thermal analysis instrument test the present embodiment that German NETZSCH company produces to passThe phase transition temperature of hot material, latent heat of phase change, the phase transformation range of testing known this phase-change heat-storage material is 392.1-404.3 DEG C, phase transformationLatent heat is 149.6J/g, and result as shown in Figure 1.
The micro-calorimeter that adopts French SETARAM company to produce, prepares with heating rate test the present embodiment of 2 DEG C/minThe specific heat capacity of high temperature heat transfer material, the test of specific heat capacity as shown in Figure 2, the specific heat capacity that shows this phase-change heat-storage material 100 DEG C-Between 270 DEG C, be rising, increase rapidly with the rising of temperature since 270 DEG C of specific heat capacities, the ratio of this material is describedThermal capacitance increases with temperature, and phase-change thermal storage ability constantly strengthens along with the rising of temperature.
Test knownly by thermogravimetric analysis, high temperature heat transfer material prepared by the present embodiment can keep stable below 800 DEG C, workBe 392.1-800 DEG C as temperature range, as shown in Figure 3, illustrate that this high temperature heat transfer material can be widely used in industrial heat energy and reclaimUtilization, solar thermal utilization etc.
Embodiment 2
A high temperature heat transfer material based on carbonate, the shared mass percent of the each component of its raw material is: manganese carbonate 33%, carbonAcid lithium 47%, potash 10%, sodium carbonate 10%.
By even above raw material ground and mixed after drying and processing, then the raw material mixing is added to crucible, be placed in resistance furnaceIn, start to be heated to its fusing and be incubated 23 hours at 500 DEG C, to ensure that raw material fully mixes; Insulation is afterwards by crucibleFrom electric furnace, take out coolingly, then pulverize, grind, obtain the high temperature heat transfer material based on carbonate.
Adopt high temperature prepared by STA-449F3 simultaneous thermal analysis instrument test the present embodiment that German NETZSCH company produces to passThe phase transition temperature of hot material, latent heat of phase change, the phase transformation range of testing known this phase-change heat-storage material is 393.3-402.8 DEG C, phase transformationLatent heat is 171Jg-1, result as shown in Figure 4.
The specific heat capacity test case of high temperature heat transfer material prepared by the present embodiment is more similar to embodiment 1, specific heat capacity 100 DEG C-Between 270 DEG C, be rising, increase rapidly with the rising of temperature since 270 DEG C of specific heat capacities, as shown in Figure 5.
Test knownly by thermogravimetric analysis, high temperature heat transfer material prepared by the present embodiment can keep stable below 800 DEG C, workBe that 393.3-800 DEG C of this high temperature heat transfer material of explanation can be widely used in industrial heat energy recycling, solar heat as temperature rangeUtilize etc.
Embodiment 3
A high temperature heat transfer material based on carbonate, the shared mass percent of the each component of its raw material is: manganese carbonate 25%, carbonic acidLithium 50%, potash 15%, sodium carbonate 10%.
By even above raw material ground and mixed after drying and processing, then the raw material mixing is added to crucible, be placed in resistance furnaceIn, start to be heated to its fusing and be incubated 22 hours at 600 DEG C, to ensure that raw material fully mixes; Insulation is afterwards by crucibleFrom electric furnace, take out coolingly, then pulverize, grind, obtain the high temperature heat transfer material based on carbonate.
Adopt high temperature prepared by STA-449F3 simultaneous thermal analysis instrument test the present embodiment that German NETZSCH company produces to passThe phase transition temperature of hot material, latent heat of phase change, the phase transformation range of testing known this phase-change heat-storage material is 394.9-404.1 DEG C, phase transformationLatent heat is 172.3Jg-1, result as shown in Figure 6.
The specific heat capacity test case of high temperature heat transfer material prepared by the present embodiment is more similar to embodiment 1, specific heat capacity 100 DEG C-Between 270 DEG C, be rising, increase rapidly with the rising of temperature since 270 DEG C of specific heat capacities.
Test knownly by thermogravimetric analysis, high temperature heat transfer material prepared by the present embodiment can keep stable below 800 DEG C, workBe 394.9-800 DEG C as temperature range, illustrate that this high temperature heat transfer material can be widely used in industrial heat energy recycling, solar energyHeat utilization etc.
Embodiment 4
A high temperature heat transfer material based on carbonate, the shared mass percent of the each component of its raw material is: manganese carbonate 30%, carbonic acidLithium 52%, potash 9%, sodium carbonate 9%.
By even above raw material ground and mixed after drying and processing, then the raw material mixing is added to crucible, be placed in resistance furnaceIn, start to be heated to its fusing and be incubated 21 hours at 600 DEG C, to ensure that raw material fully mixes; Insulation is afterwards by crucibleFrom electric furnace, take out coolingly, then pulverize, grind, obtain the high temperature heat transfer material based on carbonate.
Adopt high temperature prepared by STA-449F3 simultaneous thermal analysis instrument test the present embodiment that German NETZSCH company produces to passThe phase transition temperature of hot material, latent heat of phase change, the phase transformation range of testing known this phase-change heat-storage material is 394.1-403.3 DEG C, phase transformationLatent heat is 176Jg-1, result as shown in Figure 7.
The specific heat capacity test case of high temperature heat transfer material prepared by the present embodiment is more similar to embodiment 1, specific heat capacity 100 DEG C-Between 270 DEG C, be rising, increase rapidly with the rising of temperature since 270 DEG C of specific heat capacities.
Test knownly by thermogravimetric analysis, high temperature heat transfer material prepared by the present embodiment can keep stable below 800 DEG C, itsPhase transformation operating temperature range is 394.1-800 DEG C, illustrate this high temperature heat transfer material can be widely used in industrial heat energy recycle,Solar thermal utilization etc.
Embodiment 5
A high temperature heat transfer material based on carbonate, the shared mass percent of the each component of its raw material is: manganese carbonate 25%, carbonic acidLithium 50%, potash 15%, sodium carbonate 10%.
By even above raw material ground and mixed, then the raw material mixing is added to crucible, be placed in resistance furnace, start to be heated to itFusing is also incubated 18 hours at 600 DEG C, to ensure that raw material fully mixes; After insulation, crucible is taken out from electric furnace coldBut, then pulverize, grind, obtain the high temperature heat transfer material based on carbonate.
Adopt high temperature prepared by STA-449F3 simultaneous thermal analysis instrument test the present embodiment that German NETZSCH company produces to passThe phase transition temperature of hot material, latent heat of phase change, the phase transformation range of testing known this phase-change heat-storage material is 394.6-402.8 DEG C, phase transformationLatent heat is 173.7Jg-1, result as shown in Figure 8.
The specific heat capacity test case of high temperature heat transfer material prepared by the present embodiment is more similar to embodiment 1, specific heat capacity 100 DEG C-Between 270 DEG C, be rising, increase rapidly with the rising of temperature since 270 DEG C of specific heat capacities.
Test knownly by thermogravimetric analysis, high temperature heat transfer material prepared by the present embodiment can keep stable below 800 DEG C, workBe 394.6-800 DEG C as temperature range, illustrate that this high temperature heat transfer material can be widely used in industrial heat energy recycling, solar energyHeat utilization etc.
Claims (6)
1. the high temperature heat transfer material based on carbonate, it is characterized in that it is prepared from by raw material manganese carbonate, lithium carbonate, potash, sodium carbonate, the shared mass percent of each raw material is respectively: manganese carbonate 25%-40%, lithium carbonate 45%-60%, potash 9%-20%, sodium carbonate 9%-15%, each material content sum is 100%.
2. a kind of high temperature heat transfer material based on carbonate according to claim 1, is characterized in that described manganese carbonate, lithium carbonate, potash, sodium carbonate quality purity are all greater than 99.90%.
3. a kind of high temperature heat transfer material based on carbonate according to claim 1, its operating temperature interval is 392.1-800 DEG C.
4. according to the preparation method of the high temperature heat transfer material based on carbonate described in any one in claim 1-3, it is characterized in that comprising the steps:
(1) batching: take by mass percentage manganese carbonate 25%-40%, lithium carbonate 45%-60%, potash 9%-20%, sodium carbonate 9%-15% is as raw material;
(2) make its fusing after above-mentioned raw materials is mixed in proportion, and in molten condition insulation, it is mixed, last cooling grinding, obtains the high temperature heat transfer material based on carbonate.
5. according to the preparation method of the high temperature heat transfer material based on carbonate described in claim 4, the temperature that it is characterized in that described fusing is 500-600 DEG C.
6. according to the preparation method of the high temperature heat transfer material based on carbonate described in claim 4, it is characterized in that described temperature retention time is 18-24h.
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